JP2021502697A - Non-linear capacitors and energy storage devices containing them - Google Patents

Abstract

The present specification provides a first electrode, a second electrode, and a non-linear capacitor including a dielectric layer arranged between the first electrode and the second electrode. The dielectric layer comprises at least one organic compound having at least one electrically polarizable aromatic polycyclic conjugated core selected from copolymers, homopolymers, Sharp polymers, NLSD compounds and combinations thereof. The relationship between the capacitance C of the capacitor and the voltage between the electrodes is characterized by a monotonically increasing polynomial dependency (I) when the voltage V satisfies the inequality 0 <V≤Vmax, where the voltage Vmax is the insulation voltage Vbd If the maximum working voltage does not exceed 2 and is selected for safety reasons and the index i is in the range 2 to m, then at least one coefficient Ci is not 0 and m is 2, 3, 4, 5, or. It is 6.

Description

The present invention relates generally to passive components of electrical circuits, and particularly to non-linear capacitors and energy storage devices including them.

Energy storage is a crucial component of many types of electronic devices, especially mobile devices and vehicles, such as electric and hybrid gas-electric vehicles (also referred to herein as "hybrid vehicles"). Energy storage devices can be based on various physical effects. For example, an electric field can be used to store energy in a capacitor, and a chemical reaction (with respect to ionic motion) can be used to store energy in a battery. However, energy storage in capacitors is limited by the shape of current devices (eg, 2-D capacitor plates with limited surface area) and low dielectric constant or low dielectric insulation voltage, and batteries are electrochemically reacted. Due to the relatively slow ion motion inherent in, it can have a slow response time.

There are restrictions on current batteries. For example, current batteries can have low storage densities due to relatively low voltage (<5V) resulting from the electrochemical reaction of ions. In addition, the low motility of ions in current batteries can lead to poor charge and discharge characteristics. Moreover, the current dependence of batteries on ion transport causes high battery decomposition rates. The performance of battery-powered devices, such as hybrid or electric vehicles, can be limited by the low energy stored relative to the weight of the batteries used in such vehicles.

An important property of a dielectric material is the permittivity of the dielectric. Various types of dielectric materials are used in capacitors, including ceramics, polymer films, paper and various types of electrolytic capacitors. The most widely used polymer film materials are polypropylene and polyester. Increasing the permittivity of the dielectric makes it possible to increase the volumetric energy density, which is an important technical issue.

The second-order nonlinear optical (NLO) effects of organic molecules have been widely investigated for their advantages over inorganic crystals. Property studies include, for example, their large optical non-linearity, ultrafast response speed, high damage criteria and low absorption loss. In particular, organic thin films with excellent optical properties have tremendous potential in integrated optics such as optical switching, data manipulation and information processing. Among the organic NLO molecules, the azo dye chromophore has attracted the special interest of many researchers because of the hyperpolarizability (b) of relatively large molecules due to the delocalization of the p-electron cloud. Over the last decade, they have most often merged as guests in a polymer matrix (guest-host polymer) or grafted onto a polymer matrix (functionalized polymer).

The superelectron polarization of organic compounds is described in "Superelectron Polarization in Polymer Solids" by Roger D. Hartman and Herbert A Pohl in the Journal of Polymer Science: Part A-1 Vol. 6, pp. 1135-1152 (1968). It is described in detail. Superelectron polarization may be observed as an electron polarization external field due to the flexible interaction of excitons with charge pairs, where the charges are molecularly separated and distributed in a molecularly restricted domain. In this document, four polyacenoquinone radical polymers were investigated. These polymers have a dielectric constant of 1800-2400 at 100 Hz and are reduced to about 58-100 at 100,000 Hz. An essential drawback of the described material production methods is the use of high pressures (up to 20 kbar) to form samples for the measurement of permittivity.

Copolymers of methacrylates and methyl methacrylates containing fixed groups with two azo bonds (3RM) were prepared and their light-induced birefringence concentrations and velocities were determined by X. Meng, A Natansohn and P. Rochon. It was studied in "Azopolymers for reversible optical storage: 13. Photoorientation of fixed side chains containing two azo bonds", Polymer Vol. 38 No. 11, pp. 2677-2682, (1997). Birefringence of 0.11 was found for copolymers with 11.6 mol% azo structural units and 0.13 for copolymers with 30.0 mol% azo structural units; it contained only one azo group. Higher than the birefringence induced in poly {4'-[2- (acryloyloxy) ethyl] ethylamino} -4-nitroazobenzene [poly (DR1A)], a typical azohomopolymer containing a chromophore. The birefringence per azo structural unit for a copolymer containing 11.6 mol% 3RM is about 5 times that of a DR1A copolymer with a similar azo content, which is 3RM (high length / diameter ratio). ) Due to the unique structural characteristics. Dichroism in both the UV and visible spectrum contributes to the birefringence induced by the entire light. The rate of induced birefringence in 3RM copolymers is lower than poly (DR1A), and the birefringence stability (91-96% induced birefringence is maintained after the writing laser is turned off) is poly (DR1A) ( Better than about 80%). Good stability and slow birefringence growth rate are due to the lower motility of the large side chains.

New polymers with alkyl spacers and azobenzene groups with various substituent units are Vitaliy Smokal, Oksana Krupka, Agnesa Sinugina, and Vladimir Syromyatnikov, "Synthesis, Properties, and Research of New Push-Pluazobenzene Polymers" Mol. Cryst. Liq . Cryst., Vol. 590: pp. 105-110, (2014). Azopolymers were obtained by a two-step synthetic method. This includes the preparation of methacrylic monomers and their high molecular weight. Their photophysical and photochemical properties were investigated. The polymer was characterized and evaluated by ¹ HNMR, IR, UV spectroscopy. Thermal stability was characterized by the DSC method. The synthesized polymer exhibited a glass transition temperature in the range of 110-140 ° C.

The secondary and tertiary nonlinear optical responses of the spin-deposited thin films of the three push-pull side chain azobenzene polymers are described in Hasnaa El Ouazzani et al., "Secondary and tertiary nonlinearity of novel push-pull azobenzene polymers" by J. Phys. In Chem B, vol. 115, pp. 1944-1949 (2011), it was investigated by the second and third harmonic maker fringe methods using 30 ps laser pulses at a fundamental wavelength of 1064 nm. The measurements were made before and after aligning the chromophores by corona polling of the film, utilizing various polarization arrangements. A strong response dependence of the structure of the system was found for various charge transports within the molecule. Reported findings will be compared to previously reported results.

The synthesis of side-chain methacrylic polymers functionalized with azobenzene chromophores is described by Oksana Krupka et al., "Electronic-optical properties of novel azobenzene polymers in thin films" CHEMISTRY & CHEMICAL TECHNOLOGY, Vol. 9, No. 2, pp. , (2015), described in detail. A reversible change in thin film absorption is observed when irradiating it with monochromatic, linearly polarized light under the application of an external DC field. The amount of change depends on the angle between the photopolarization and the direction of the DC electric field.

U.S. Patent Application No. 15 / 043,247 U.S. Patent Application 15 / 449,587 U.S. Patent Application No. 15 / 710,587 U.S. Patent Application 15 / 469,126 U.S. Patent Application No. 15 / 090,509

Journal of Polymer Science: Part A-1 Vol. 6, pp. 1135-1152 (1968) Polymer Vol. 38 No. 11, pp. 2677 --2682, (1997) Mol. Cryst. Liq. Cryst., Vol. 590: pp. 105-110, (2014) J. Phys. Chem B, vol. 115, pp. 1944-1949 (2011) CHEMISTRY & CHEMICAL TECHNOLOGY, Vol. 9, No. 2, pp. 137 --141, (2015)

Capacitor-based energy storage devices are known to have well-known advantages over, for example, battery electrochemical energy storage devices. However, ordinary energy storage devices based on capacitors often do not store energy in smaller volumes or weights or at lower energy storage costs than batteries, making capacitors unrealizable in some applications, such as electric vehicles. to enable. Compared to batteries, the disclosed solid-state energy storage devices allow energy to be stored at significantly higher electrical densities, ie charge / discharge rates, and have a long life with little decomposition, hundreds, numbers. It can be charged and discharged (cycled) thousands or millions of times.

The present invention provides a non-linear capacitor including a first electrode, a second electrode, and a dielectric layer arranged between the first electrode and the second electrode. The dielectric layer comprises at least one organic compound having at least one electrically polarizable aromatic polycyclic conjugated core selected from copolymers, homopolymers, Sharp polymers, NLSD compounds and combinations thereof. .. If the relationship between the capacitance C of the capacitor and the voltage V between the electrodes satisfies the inequality 0 <V ≤ V _max , then the voltage V
Characterized by the monotonically increasing polynomial dependence of
The voltage V _max is the maximum working voltage that does not exceed the insulation voltage V _bd and is selected for safety reasons, where at least one coefficient C _i is not 0 for a value in the range i 2 to m. , M is 2, 3, 4, 5, or 6.

In another aspect, the invention comprises an energy storage device comprising a non-linear capacitor whose capacitance is power dependent on the above voltage and using power electronics at voltages in the range V _max 200 volts to V _max 1000 volts. provide. In some examples, the energy storage device may be operated at a V _max greater than 1000 volts.

Incorporation of References All publications, patents, and patent applications referred to herein shall be incorporated by reference in their respective publications, patents, or patent applications, specifically independently. To the same extent incorporated herein by reference.

The organic compound is described in US Patent Application No. 15 / 043,247 (Attorney Docket Number CSI-046), filed February 12, 2016; Sharp Polymer; filed March 3, 2017. Generally described in US Patent Application No. 15 / 449,587 (Attorney Docket Number CSI-050B) and US Patent Application No. 15 / 710,587 (Attorney Docket Number CSI-050C) filed on September 9, 2017. Yanli Polymer; Non-linear dielectric material generally described in US Patent Application 15 / 469,126 (Attorney Docket Number CSI-050) filed March 24, 2017; US filed April 4, 2016. Electricity generally described in Patent Application 15 / 090,509 (Attorney Docket Number CSI-051) and US Patent Application 15 / 163,595 (Attorney Docket Number CSI-051B) filed May 24, 2016. Patentably polarizable compounds may be incorporated and incorporated by reference, which describe the polarizable organic compounds of a typical complex and are electrically polarizable aromatics throughout the specification. Referenced as a ring-conjugated core.

All of the description forms part of the invention, with the accompanying figures and details, so that the more complete evaluation of the invention and its advantages can be better understood with reference to the detailed description below. It will be easily achieved, considering the connection with the explanation. Embodiments of the present invention are shown in the figure below for illustrative purposes only:
The relationship between the charge Q on the electrode of the capacitor and the voltage V applied to the electrode is shown graphically. The capacitors disclosed in flat and flat electrodes are shown graphically. The capacitors disclosed in the wound (round) electrodes are shown graphically. It is schematically shown how the charge Q on the electrode of the capacitor depends on the voltage applied to the electrodes of the nonlinear capacitor (F) and the linear capacitor (D). An energy storage battery using the energy storage device according to the aspect described in the present invention is shown graphically. An example of a capacitive energy storage module having two or more networked energy storage batteries according to an alternative embodiment described in the present invention is shown. An example of a capacitive energy storage system having two or more energy storage networked modules according to an alternative embodiment described in the present invention is shown.

Although various embodiments of the present invention are shown and described herein, it will be apparent to those skilled in the art that such embodiments are provided for purposes of illustration only. Many variations, changes and substitutions may occur for those skilled in the art without departing from the present invention. It should be understood that various alternatives may be used in the embodiments of the invention described herein.

The present invention provides the above-mentioned nonlinear capacitor. In one embodiment of a non-linear capacitor, the working voltage range is from V _int to V _max , where V _int is the tangent at the point where the dependent Q (V) = C (V) · V is V = V _max. Determined by the intersection of a straight line with the horizontal axis, the difference between V _max and V _int is defined by the ratio below.

In another embodiment of the invention, electrically polarizable aromatic polycyclic conjugated cores interact with each other by dipole and π-π interactions to form a molecular stack, where the organic compound is a polymer backbone or conjugated. It further contains an alkyl tail substituent attached to Sharp and NLSD molecular compounds. The alkyl tail substituents also interact by hydrophobic interactions to form a covering that surrounds and separates the molecular stack, providing solubility of the organic compound and a dielectric layer at the working voltage applied to the electrodes of the capacitor. Prevents electron avalanche insulation. In yet another embodiment of the invention, the electrically polarizable aromatic polycyclic conjugated core comprises a benzene ring attached to a linker group and is described by the following structural formula:
Here, L is a linker group selected from −N = N−, −CC− (alkyne), and −C = C−, and n = 0, 1, 2, 3, 4, 5 and 6. .. In yet another embodiment of the invention, the electrically polarizable aromatic polycyclic conjugated core is an electrophilic group (acceptor) and / or a nucleophilic group (acceptor) located at the terminal and / or side (lateral) plane. Donors) are further included. Electrophilic group (acceptor) is, -NO _2, -NH ₃ ^+, and -NRR'R "(quaternary nitrogen salts), the counter ion Cl ^- or Br ^-, -CHO (aldehyde), - CRO (keto group) , -SO ₃ H (sulfonic acid), -SO ₃ R (sulfonate), -SO ₂ NH ₂ (sulfonamide), -COOH (carboxylic acid), -COOR (ester, from the carboxylic acid side), -COCl (carboxylic acid) Selected from-CONH ₂ (from the amide, carboxylic acid side), -CF ₃ , -CCl ₃ , and -CN, R is alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl). Etc.), allyl (-CH ₂ -CH = CH ₂ ), benzyl (-CH ₂ C ₆ H ₅ ) group, phenyl (+ substituted phenyl) and other aryl (aromatic) groups selected from the list. And R'and R'are selected independently from the list of R groups. Nucleophile (donor) is, ^-O - (phenoxide such -ONa or _{-OK), - NH 2, -NHR} , -NR 2, -OH, OR ( ether), - NHCOR (amide, amine side) , -OCOR (esters, alcohols side) alkyl, -C ₆ H _5, 'is selected from, R and R' vinyl, and NRR are alkyl (methyl, ethyl, isopropyl, tert- butyl, neopentyl, cyclohexyl ), Allyl (-CH ₂ -CH = CH ₂ ), benzyl (-CH ₂ C ₆ H ₅ ) group, phenyl (+ substituted phenyl) and other aryl (aromatic) groups selected independently from the list. It is a group.

The presence of electrophilic groups (acceptors) and nucleophilic groups (donors) in aromatic polycyclic conjugated molecules means that the non-uniform distribution of electrical density in the conjugated molecules: electron surplus and electron surplus in one place (donor region). Deficiency of electrons in other places (acceptor region): promotes. The effect of the external electric field on the non-uniform distribution of electrical densities associated with conjugated molecules leads to inductive polarization _Pind . In the general case, inductive polarization is a non-linear function of the intensity of the local electric field E _loc . In the weak nonlinear assumption, it is possible to approximate the induced polarization _Pind by some decomposition conditions of the polarization induced by a series of degrees of local electric field intensity. In such cases, the induced polarization of the environment (eg, of the molecule) can be described by the following equation:
Here, α is a linear polarizability and β is a square polarizability. Although the assumption of small electric field is not always correct, the α and β parameters may nevertheless be used in the analysis of the polarizability properties of the compounds of the present invention. In the present invention, the method of increasing the induced polarization of the described compounds, and thus the method of increasing the linear polarizability α and the square polarizability β, is of particular interest. Such attention is caused by the dipole and quadrupole electric moment constants being neutralized with each other by the self-assembly of such conjugated molecules. The analysis depends on the magnitude of the average electrical density in the molecule, and the nonlinear polarizability depends on the magnitude of the inhomogeneity of the electrical density. It has also been shown that the non-central symmetric orientation of the electron donor and acceptor groups can lead to a strong non-linear response of the electrical polarization of the compound in the presence of an electric field. The effects of chemical structure on linear polarizability α and square polarizability β are shown in Table 1.

Table 1 shows that the arrangement of electron donating groups and electron attracting groups on the electron conjugated system is important for increasing polarizability. In addition, the structures in Table 1 show conjugated ring systems that may be further modified to enhance polarizability. However, they are unrestricted examples and require additional resistance substituents (tails) to achieve high resistivity.

In another embodiment of the invention, at least one tail substituent is − (CH ₂ ) _n CH ₃ , −CH ((CH ₂ ) _n CH ₃ ) ₂ ) (n is 1 or greater), alkyl, aryl, and. Substituted alkyl, substituted aryl, branched alkyl, branched aryl, cyclic alkyl group complex, −X ＝ CH (CH ₂ ) _n CH ₃ , −CC (CH ₂ ) _n CH ₃ , −X ＝ C ((CH ₂ ) _n Selected independently from the list containing CH ₃ ) ((CH ₂ ) _m CH ₃ ) and combinations thereof, the alkyl group is from a methyl group, an ethyl group, a propyl group, a butyl group, an i-butyl group and a t-butyl group. Selected, the aryl group is selected from phenyl, benzyl and naphthyl groups, X is C, S or N and n and m are independently selected from 1-20. In yet another embodiment of the invention, it is selected from YanLi materials having the following structures 1-26 as shown in Table 2 below.

In one embodiment of the nonlinear capacitor described, the voltage V _int is the derivative.
When increases, it approaches the maximum voltage V _max . In another embodiment of the nonlinear capacitor described, the ratio (V _max −V _int ) / V _max is less than 0.1. In yet another embodiment of the described non-linear capacitor, until the charge Q on the electrode changes in the range between charge Q _int = Q (V _int ) and maximum charge Q _max = Q (V _max ). The voltage V applied to the electrodes is approximately constant during charging / discharging of the non-linear capacitor and varies in the range between the voltage V _int and the voltage V _max . In another embodiment of the described non-linear capacitor, the organic compound is characterized by an inductive polarization _Pind that may be described in the form of decomposition to a series of degrees of intensity of the local electric field E _loc :
Where α is the linear polarizability and β is the square polarizability.

The present invention provides the above energy storage device.

In order to understand the present invention more easily, the following figure is referred to for the purpose of assisting the understanding of the present invention, but without the intention of limiting the scope of claims.

FIG. 1 graphically shows the relationship between the charge Q = C (V) · V on the electrode of the capacitor and the voltage applied to the electrode (see curve A). The charge Q is when the voltage V satisfies the inequality 0 <V ≤ V _max .
Due to the monotonously increasing polynomial dependence of, the voltage V depends non-linearly, where the voltage V _max is the maximum working voltage not exceeding the insulation voltage V _bd and is chosen for safety reasons and the coefficient Q _i , I-th order charge Q non-linearity, m is 1, 2, 3, 4, 5, or 6, and Q _max characterizes Q (V _max ). The straight line 2 is a tangent to the nonlinear dependent Q (V) when the voltage V is equal to the maximum voltage, that is, when V = V _max . This straight line B intersects the horizontal axis at the point of V = V _int , and the charge corresponding to this voltage is equal to Q _int = Q (V _int ). The following ratios are made due to the difference between the two voltages V _max and V _int .

From the above equation, the difference V _max −V _int results in a decrease with increasing non-linear dependent gradient at the maximum voltage V _max . During charging / discharging of the capacitor, the voltage V changes at intervals between V _max and V _int , while the charge Q changes between Q _max and Q _int .

The present invention provides a non-linear capacitor that is arranged parallel to each other and contains two metal electrodes, rolled or flat and flat, and a dielectric layer between the electrodes. The dielectric layer comprises at least one organic compound having at least one electrically polarizable aromatic polycyclic conjugated core selected from copolymers, homopolymers, Sharp polymer NLSD compounds and combinations thereof.

As shown in FIG. 2A, the non-linear capacitor includes a first electrode 1, a second electrode 2, and a dielectric layer 3 arranged between the first electrode and the second electrode. Electrodes 1 and 2 may be made of a metal such as copper, zinc or aluminum, or other conductive material and are generally in planar form.

Electrodes 1 and 2 are flat and flat and are arranged parallel to each other. Alternatively, the electrodes may be flat and parallel, not necessarily flat, in a coiled, rolled, curved, folded, or form that reduces factors in all forms of the capacitor. It may be in a state. The electrodes may be non-flat, non-planar, non-parallel, or a combination of two or more of them. For illustrative purposes and without limitation, the spacing between electrodes 1 and 2 may range from about 100 nm to about 10000 μm. The maximum voltage V _bd between the electrodes 1 and 2 is the approximate product of the breaking electric field E _bd and the electrode spacing d. If the E _bd is 0.1 V / nm and the distance d between the electrodes 1 and 2 is 10000 μm (100,000 nm), the maximum voltage V _bd can be 100,000 volts.

The electrodes 1 and 2 may have the same shape, the same dimensions, and the same area A as each other. The area A of each of the electrodes 1 and ² may be in the range of about 0.01 m ² to about 1000 m ² for the purpose of exemplifying and not limiting. These ranges are not limited. Other ranges of electrode spacing d and area A are within the scope of aspects of the present invention.

The present invention includes, for example, a coiled nonlinear capacitor, as shown in FIG. 2B. In this example, the capacitor 20 includes a first electrode 21, a second electrode 22, and a dielectric material layer 23 of the type described above arranged between the first and second electrodes. The electrodes 21 and 22 may be made of a metal such as copper, zinc or aluminum or other conductive material and are generally planar in shape. In one embodiment, the electrode and dielectric material layer 23 are in the form of a long piece of material that is sandwiched together and sown in a coil with a separating material of, for example, a plastic film, such as polypropylene or polyester, and the electricity between the electrodes 21, 22 Suppress short circuit.

FIG. 3 shows at least one organic having at least one electrically polarizable aromatic polycyclic conjugated core selected from standard material (D) and copolymers, homopolymers, Sharp polymers, NLSD compounds and combinations thereof. The dependence (QV plot) of the charge (Q) accumulated on the electrode with respect to the voltage (V) contained in the apparatus is shown with respect to the material (F) of the dielectric layer having the compound.

Referring to FIG. 3, the total energy stored in the exemplary device is, for example, (a) the maximum achievable voltage beyond the electrodes of the device, V _max , (b) on the electrodes of the device at this voltage. It may depend on the stored charge, Q _max and / or the formation of a QV curve for the device (c). Generally, the total energy stored in the device, E, is given by equation (I).

Without limitation, the energy (and energy density) stored in the device may be increased in at least three ways: increasing breaking voltage, increasing dielectric constant ε of the dielectric material of higher order dielectric layers, And the increase in area under the QV curve.

The maximum voltage V _max can be limited by the maximum voltage that can be supported by the device, i.e. the breaking voltage V _bd . A device designed to increase V _max can increase the breaking voltage V _bd .

In general, the energy stored in the device is equal to the area under the QV curve in the plot as shown in FIG. For most materials, the electrical capacity does not depend on Q (ie V (Q) = Q / C as indicated by the dotted line "D" in FIG. 3) and the energy stored in the device is the equation (ie). Given by II).

If C depends on Q, the shape of the curve in FIG. 3 may allow an increase in stored energy up to C * V _max ² , which is twice the stored energy for most materials.

The area under the QV curve may be increased by including a dielectric material that is non-linearly dependent on the permittivity with respect to V.

One or more capacitors of the type shown in FIG. 2A or FIG. 2B may be used in an energy storage battery. In FIG. 4, for purposes of illustration and not limiting, a possible implementation of an energy storage battery 40 of the type shown in FIG. 2B, including, for example, a capacitive energy storage device of one or more capacitors 20, DC. It is connected to the voltage converter 41. One high-order capacitor is simply depicted, but in other practices, the capacitive energy storage of two or three or more high-order capacitors in a combination of capacitor networks and / or parallels for various types. The combination of batteries 40 may be connected to the voltage converter 41.

In yet another embodiment, the capacitive energy storage battery 40 may further include a cooling device 42. In some practices, cooling may be passive using, for example, radiative cooling vanes on the capacitive energy storage device 40 and the DC voltage converter 41. Alternatively, a fluid such as air, water or ethylene glycol can be used as a coolant in the active cooling system. For purposes of illustration and not limiting, the cooling system 30 may include a heat conduit in contact with the capacitive energy storage device 20 and the DC voltage converter 41. The conduit is filled with a heat exchange medium, which may be solid, liquid or gas. In some practices, the cooling mechanism may include a heat exchanger 44 composed of heat extracted from the heat exchange medium. In another embodiment, the cooling mechanism 41 includes a conduit in the form of cooling blades on the capacitive energy storage device 20 and the DC-voltage converter 41, and the heat exchange medium is blown from the cooling blades, for example by a blower. It's air. In another embodiment of the invention, the heat exchanger 44 may include a phase change heat pipe configured to provide cooling. The cooling performed by the phase change thermal pipe is a solid to liquid phase change of the phase change material (eg using melting of ice or other solid), or a liquid to gas (eg by volatilization of water or alcohol). It may be about the phase change of. In yet other embodiments, the conduit or heat exchanger 44 may include a container containing a material that undergoes a solid-to-liquid phase change, such as paraffin wax.

As an aspect of the present invention, for example, a capacitive energy storage module 50 as shown in FIG. In the example shown, the energy storage module 50 includes two or more energy storage batteries 40 of the type described above. Each energy storage battery is a capacitive energy storage device 46 having one or more capacitors 48 and a DC-voltage converter 41, which may be a back converter, boost converter, or back / boost converter. including. In addition, each module has, for example, a microprocessor, a microcontroller, an application-specific integrated circuit (ASIC), a field programmable gate array (FPGA), a coupled programmable logic circuit (CPLD), and the ability to execute closed-loop control processes. and appropriate logic circuitry (optionally) a communication interface, as well as, for example, inflow voltage _{V in} and out voltage _{V out} related to the voltage sensor V, current from / to the capacitive energy storage device 46 _{I sd} and / or DC Current sensor A for current I _vc from / to voltage converter 41, capacitive energy storage and / or temperature sensor on DC-voltage converter, analog coupled with sensor on DC voltage converter 41 A control panel 49 including a digital converter may be included. In some practices, the control panel 49 may be integrated into the DC-voltage converter 41. The DC-voltage converter 41 may include a back regulator, a boost regulator, a separate inflow / outflow back and boost regulator, a bidirectional boost / back regulator or a split-pi converter and controls. The board 49 may be configured to maintain a constant outflow voltage V _out from the DC-voltage converter while discharging and / or charging the capacitor with an approximately constant current while maintaining a stable inflow voltage. .. The DC-voltage converter 41 and the control panel 49 may be configured to maintain the voltage within a desired range. For purposes of illustration and without limitation, the control panel 49 may be based on a controller for a bidirectional back / boost transducer. In such an arrangement, the control panel 59 stabilizes the outflow voltage of the DC-voltage converter with a code that forms an appropriate control loop. An example of a possible control loop is described in US Pat. No. 2,017,237,271, which is incorporated herein by reference.

The operation specifications of the control panel 49 depend somewhat on the type of back / boost converter used in the DC-voltage converter 41. For example, buck / boost converter, a surface of the inflow voltage inflow side and the coil connected to the V _in, single with high-side switch of the outlet side which is connected on the other side which is connected to ground or common voltage It may be a switch converter of. Capacitors are coupled across the outflow voltage V _out . The pulsed switch signal changes the on and off switches. The outflow voltage depends on the load cycle that switches the signal. For illustration purposes, the switch is used for voltage and / or current requirements of DC-voltage converters for energy storage, such as MOSFET equipment, stacked MOSFET equipment, IGCT equipment, high drain-source voltage Sic MOSFET equipment, etc. It may be embedded as a dependent, gated switch device. In the case of a gate switch device, the control panel provides a signal to the gate terminals of the switch device. The control panel 49 exercises this type of back / boost transducer to step down (back) or boost (boost) by adjusting the load cycle of the switch signal.

The module 50 includes an interconnect system that connects the anode and cathode of the individual energy storage batteries, creating a general anode and general cathode for the capacitive energy storage module. In some implementations, the interconnect system may include a parameter bus 52 and a power switch PSW. Each energy storage battery 40 in the module 50 may be connected to the parameter bus 52 via the power switch PSW. These switches allow for two or more modules that are selectively coupled in parallel or in series via two or more rails, which can serve as general anodes and general cathodes. The power switch also allows for one or more energy storage batteries separated from the module, eg, battery duplication and / or maintenance without module shutoff operation. The power switch PSW may be based on solid-state power switch technology or may be performed by an electrochemical switch (eg, a relay) or some combination of the two.

In some implementations, the energy storage module 50 further includes a power meter 54 to monitor power inflows or outflows into the module. In some implementations, the energy storage module further includes a networked configured control node 55 to control power outflows from the module and power inflows into the module. The networked control nodes 55 allow each module to exchange information with the system control computer over a high speed network. The networked control node 55 includes a voltage control logic circuit 56 to be set, and selectively operates each voltage controller 41 in each energy storage battery 40, for example, via a separate control panel 49. To control. The control node 55 may also include the set switch control logic circuit 57, and controls the operation of the power switch PSW. The control panel 49 and the power switch PSW may be connected to the control node 55 via the data bus 58. The voltage control and switch logic circuits within the networked control node 55 can be one or more microprocessors, microcontrollers, application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), or coupling programmable. It may be executed by a logic circuit (CPLD). The control node 55 may include a network interface 59, facilitating the transport of signals between the voltage control logic 57 and the control panel 49 on the individual energy storage batteries 40 and switching via the data bus 58. It also transports signals between the logic circuit 56 and the power switch PSW.

According to yet another aspect of the invention, the capacitive energy storage system may include, for example, two or more networked capacitive energy storage modules of the type shown in FIG. One embodiment of such a capacitive energy storage system 60 is shown in FIG. The system 60 includes two or more energy storage modules 50 of the type shown in FIG. Each capacitive energy storage module 50 includes, for example, two or more energy storage batteries 40 of the type shown in FIG. 4, connected by an interconnect system 52 and controlled by a control node 55. Each capacitive energy storage module may also include a module electricity meter 54. Although not shown in FIG. 6, each control node 55 may include a voltage control logic circuit 56, which controls a voltage controller in each capacitive energy storage battery 40 and switch logic circuit 57, as described above. The module controls the internal power switch. In addition, each control node 55 includes an internal data bus 58 and a network interface 59, which may be installed and connected as described above. Power to and from the capacitive energy storage module 50 is connected to the system power bus 62 via the system power switch SPSW and is based on solid state power switch technology or an electrochemical switch (eg relay) or It may be performed by some combination of the two. In some implementations, there may be an inverter (not shown) connected between the respective capacitive energy storage modules 50 and system power bus 62, and DC power from the modules to AC power and vice versa. Convert.

The system 60 includes a system controller 66 connected to the system data bus 68. The system controller may include a switch control logic 63, a voltage control logic 61, and a system network interface 64. The voltage control logic 60 may be configured to control the operation of individual DC-voltage controllers within the individual batteries 40 of the individual modules 50. The switch control logic 63 may be configured to control the operation of the system power switch SPSW and the power switch PSW within the individual capacitive energy storage modules 50. The power control signal is transmitted from the power control logic 63 through the network interface 64, the system data bus 68, and the module network interface 69 of the control node 46 with respect to the specific module, the module data bus 68, and the control panel 59 of each battery 50. It may be sent to a specific DC controller 41 in a specific capacitive energy storage battery 40 of a specific capacitive energy storage module.

For purposes of illustration and not limiting, the system controller 66 may be a deterministic controller, an asynchronous controller, or a controller with a distributed clock. In a particular embodiment of the capacitive energy storage system 60, the system controller 66 may include a distributed clock set and one or more of the capacitive energy storage modules 50 of one or more. Synchronize the movement of several independent voltage changers in the energy storage battery.

Aspects of the present invention allow for electrical energy storage on a larger scale than is possible with conventional electrical energy storage systems. Extensive energy storage is met by selectively connecting one or more capacitors to a battery, connecting two or more batteries to a module, or connecting two or more modules to a system in a DC-voltage converter. obtain.

Although the present invention has been described in detail with reference to certain preferred embodiments, those skilled in the art relating to the present invention have made various changes and enhancements without departing from the gist and scope of the subsequent claims. You will recognize that it is also good. The preferred or unfavorable properties may be combined with other preferred or unfavorable properties. It is understood that various alternatives to the embodiments of the invention described herein can be used in the practice of the invention. The following claims are intended to define the scope of the invention, the methods and structures within the scope of these claims, and the equivalents contained therein.

1: Electrode 2: Electrode 3: Dielectric layer 20: Capacitor 21: First electrode 22: Second electrode 23: Dielectric material layer 40: Capacitive energy storage battery 41: DC voltage converter 42: Cooling device 43: Control panel 44: Heat exchanger 46: Capacitive energy storage device 48: Capacitor 49: Control panel 50: Energy storage module 52: Parameter bus 53: Control panel 54: Power meter 55: Control node 56: Voltage logic circuit 57: Switch logic Circuit 58: Data bus 59: Network interface 60: Energy storage system 61: Voltage control logic 62: System power bus 63: Switch control logic 64: Network interface 66: System controller 68: System data bus

Claims (15)

A non-linear capacitor comprising a first electrode, a second electrode, and a dielectric layer disposed between the first electrode and the second electrode.
The dielectric layer comprises at least one organic compound having at least one electrically polarizable aromatic polycyclic conjugated core selected from copolymers, homopolymers, Sharp polymers, NLSD compounds and combinations thereof.
When the relationship between the capacitance C of the capacitor and the voltage V between the first electrode and the second electrode satisfies the inequality 0 <V ≤ V _max .
Characterized by the monotonically increasing polynomial dependence of
The voltage V _max is the maximum working voltage that does not exceed the insulation voltage V _bd , is selected for safety reasons, and when the exponent i is in the range 2 to m, at least one coefficient C _i is not 0. m is a non-linear capacitor of 2, 3, 4, 5, or 6. The voltage range is from V _int to V _max ,
The difference between the voltages V _max and V _int is determined by the intersection of the horizontal axis and the straight line that is the tangent to the dependent Q (V) = C (V) · V at the point where V _int becomes V = V _max. The non-linear capacitor according to claim 1, defined by the following ratio.
The electrically polarizable aromatic polycyclic conjugated cores interact with each other by dipole and π-π interactions to form a molecular stack.
The organic compound further comprises an alkyl tail substituent that binds to the polymeric backbone or conjugated Sharp and NLSD molecular compounds.
The alkyl tail substituents interact with each other by hydrophobic interaction to form a covering that surrounds and separates the molecular stack, providing solubility of the organic compound and at the working voltage applied to the electrodes of the capacitor. Preventing electron avalanche insulation of the dielectric layer,
The non-linear capacitor according to claim 1. The non-linear capacitor according to claim 1, wherein the electrically polarizable aromatic polycyclic conjugated core contains a benzene ring bonded to a linker group and is described by the following formula.
(Here, L is a linker group selected from −N = N−, −CC− (alkyne), and −C = C−, at n = 0, 1, 2, 3, 4, 5 and 6. is there) Claim 1 wherein the electrically polarizable aromatic polycyclic conjugated core further comprises an electrophilic group (acceptor) and / or a nucleophilic group (donor) located on the terminal and / or side (lateral) planes. The non-linear capacitor described. The electrophilic group (acceptor) is, -NO _2, -NH ₃ ^+, and -NRR'R "(quaternary nitrogen salts), the counter ion Cl ^- or Br ^-, -CHO (aldehyde), - CRO (keto group ), -SO ₃ H (sulfonic acid), -SO ₃ R (sulfonate), -SO ₂ NH ₂ (sulfonic amide), -COOH (carboxylic acid), -COOR (ester, from the carboxylic acid side), -COCl ( Carboxylic acid chloride), -CONH ₂ (amide, from the carboxylic acid side), -CF ₃ , -CCl ₃ , and -CN
R is alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl, etc.), allyl (-CH ₂ -CH = CH ₂ ), benzyl (CH ₂ C ₆ H ₅ ) group, phenyl (+ substituted phenyl) The nonlinear capacitor according to claim 5, wherein the group is selected from a list containing and other aryl (aromatic) groups, where R'and R "are independently selected from the list of R groups. It said nucleophile (donor) is, ^-O - (phenoxide such -ONa or _{-OK), - NH 2, -NHR} , -NR 2, -OH, OR ( ether), - NHCOR (amide, amine side ), -OCOR (from the ester, alcohol side), alkyl, -C ₆ H ₅ , vinyl, and NRR',
R and R'are alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl, etc.), allyl (-CH ₂ -CH = CH ₂ ), benzyl (CH ₂ C ₆ H ₅ ) groups, phenyl (+). The nonlinear capacitor according to claim 5, which is a group independently selected from the list containing substituted phenyl) and other aryl (aromatic) groups. At least one tail substituent is − (CH ₂ ) _n CH ₃ , −CH ((CH ₂ ) _n CH ₃ ) ₂ ) (n is 1 or more), alkyl, aryl, substituted alkyl, substituted aryl, branched alkyl, Branched aryl, cyclic alkyl group complex, −X ＝ CH (CH ₂ ) _n CH ₃ , -CC (CH ₂ ) _n CH ₃ , −X ＝ C ((CH ₂ ) _n CH ₃ ) ((CH ₂ ) _m Selected independently from the list containing CH ₃ ) and combinations thereof
The alkyl group is selected from methyl group, ethyl group, propyl group, butyl group, i-butyl group and t-butyl group, the aryl group is selected from phenyl group, benzyl group and naphthyl group, and X is C, S. Or N, where n and m are independently selected from 1 to 20, the non-linear capacitor according to claim 3. The nonlinear capacitor of claim 1, wherein the copolymer is selected from YanLi materials having structures 1-26 below.
The voltage V _int is the derivative
The nonlinear capacitor according to claim 2, wherein when the voltage increases, the maximum voltage V _max is approached. The nonlinear capacitor according to claim 2, wherein the ratio (V _max −V _int ) / V _max is less than 0.1. The voltage applied to the electrode (in between) until the charge Q on the electrode changes in the range between charge Q _int = Q (V _int ) and maximum charge Q _max = Q (V _max ) is the capacitor. The non-linear capacitor according to claim 2, which is approximately constant during charging / discharging and varies in the range between voltage V _int and voltage V _max . The non-linear capacitor according to claim 1, wherein the organic compound is characterized by an inductive polarization _Pind that is approximated by decomposition to a series of degrees of intensity of the local electric field E _loc .
(Α is linear polarizability, β is square polarizability) An energy storage device comprising the non-linear capacitor according to claim 1, wherein the electric capacity is power dependent on the voltage, and using power electronics at a voltage in the range of V _max 200 volts to V _max 1000 volts. An energy storage device comprising the non-linear capacitor according to claim 1, wherein the electrical capacity is power dependent on the voltage, using power electronics, and operating at a V _max voltage greater than 1000 volts.